Tyrosine nitration of human ERK1 introduces an intra-hydrogen bond by molecular dynamics simulations

Structural Chemistry - ERK1 is an important kinase in Ras–Raf–MEK signaling. We have recently demonstrated by mass spectrometry that Tyr210 of ERK1 can be nitrated, and the nitration...     

Desingularization of a Steady Vortex Pair in the Lake Equation

Potential Analysis - We construct a family of steady solutions of the lake model perturbed by some small Coriolis force, that converge to a singular vortex pair. The desingularized solutions are...     

Above,below, and in‐between the two glass transitions of ultrathin free‐standing polystyrene films: Thermal expansion coefficient and physical aging

In previous work we observed two simultaneous transitions in high molecular weight (MW) free‐standing polystyrene films that were interpreted as two thickness‐dependent reduced glass transition temperatures (T_gs). The weaker lower transition agreed well with the MW‐dependent T_g(h) previously reported, while the much stronger upper transition matched the MW‐independent T_g(h) previously observed in low‐MW free‐standing films. Here, we investigate the nature of these two transitions by inspecting the temperature dependence of the films' thermal coefficient of expansion (TCE) and present physical aging measurements using ellipsometry both below and in‐between the two transitions. TCE values indicate approximately 80 to 90% of the film solidifies at the upper transition, while only 10 to 20% remains mobile to lower temperatures, freezing out at the lower transition. Physical aging is observed at a temperature below the upper transition, but above the lower transition, indicative of the upper transition being an actual glass transition associated with the α‐relaxation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 64–75     

Ambiguous anti-fouling surfaces: Facile synthesis by light-mediated radical polymerization

In an attempt to create a polymer brush-based platform for the systematic study for anti-biofouling surfaces, the benefits of surface initiated, visible light-mediated radical polymerization are utilized to fabricate well-defined, chemically ambiguously patterned surfaces. A variety of analytical tools are used to illustrate the precise tuning of surface chemistry and thoroughly characterize spatially well-defined, hydrophilic/hydrophobic surfaces composed of poly(ethylene glycol methacrylate) and poly(trifluoroethyl methacrylate) with chemical definition on the micron scale. Advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization are combined to achieve both high spatial control and expanded monomer tolerance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 253–262     

Kβ X-Ray Emission Spectroscopic Study of a Second-Row Transition Metal (Mo) and Its Application to Nitrogenase-Related Model Complexes

In recent years, X-ray emission spectroscopy (XES) in the Kβ (3p-1s) and valence-to-core (valence-1s) regions has been increasingly used to study metal active sites in (bio)inorganic chemistry and catalysis, providing information about the metal spin state, oxidation state and the identity of coordinated ligands. However, to date this technique has been limited almost exclusively to first-row transition metals. In this work, we present an extension of Kβ XES (in both the 4p-1s and valence-to-1s [or VtC] regions) to the second transition row by performing a detailed experimental and theoretical analysis of the molybdenum emission lines. It is demonstrated in this work that Kβ₂ lines are dominated by spin state effects, while VtC XES of a 4d transition metal provides access to metal oxidation state and ligand identity. An extension of Mo Kβ XES to nitrogenase-relevant model complexes shows that the method is sufficiently sensitive to act as a spectator probe for redox events that are localized at the Fe atoms. Mo VtC XES thus has promise for future applications to nitrogenase, as well as a range of other Mo-containing biological cofactors. Further, the clear assignment of the origins of Mo VtC XES features opens up the possibility of applying this method to a wide range of second-row transition metals, thus providing chemists with a site-specific tool for the elucidation of 4d transition metal electronic structure.